JPH0482886A - New vinyl compound - Google Patents

Abstract

NEW MATERIAL:N-Methyl-N-2-(1,3-dioxolan-2-yl)ethylacrylamide expressed by formula I. USE:A raw material monomer for heat-sensitive polymer compounds, utilizable as light shielding substances, temperature sensors, adsorbents, toys, interiors, printing agents, displays, separation membranes and mechanochemical materials and capable of causing phase transition in water and alcoholic solvents. PREPARATION:Acryloyl chloride expressed by formula II is reacted with N- methyl-2-aminoethyl-1,3-dioxolane expressed by formula III and triethylamine in a solvent at 0-10 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a novel vinyl compound. More specifically, the present invention provides heat-sensitive materials that undergo a phase transition in water or alcohol solvents and can be used in light shielding bodies, temperature sensors, adsorbents, toys, interior decorations, textile printing agents, displays, separation membranes, and mechanochemical materials. This invention relates to vinyl compounds suitable as raw material monomers for polymeric compounds.

[Conventional technology]

Some water-soluble polymer compounds exhibit a special reversible dissolution behavior in which they precipitate and become cloudy above a certain temperature (transition temperature or cloud point) in an aqueous solution state, and dissolve and become transparent below that temperature. This compound is also called a hydrophilic-hydrophobic thermoreversible polymer compound or a heat-sensitive polymer compound, and has recently attracted attention as a material for light shields in greenhouses, temperature sensors, and water-soluble organic substance adsorbents. It's starting to look like this.

As heat-sensitive polymer compounds such as -2= -τ-, partially saponified polyvinyl acetate, polyvinyl methyl ether, methylcellulose, polyethylene oxide, polyvinylmethyloxacilidinone, and polyacrylamide derivatives have been known so far. There is.

Among these heat-sensitive polymer compounds, polyacrylamide derivatives are particularly useful because they are stable in water and can be produced at relatively low cost, and so far poly(N-ethyl acrylamide) has been used. Poly(N-n-propyl(meth)acrylamide), Poly(N-isopropyl(meth)acrylamide), Poly(N-cyclopropyl(meth)acrylamide)
acrylamide), poly (N,N-diethylacrylamide), poly (N-methyl-N-ethylacrylamide), poly (N-methyl-N-n-propylacrylamide), poly (N-methyl-N-isopropylacrylamide) , poly(N-acryloylpiperidine)
, poly (N-acryloylpyrrolidine), poly (N
-tetrahydrofurfuryl (meth)acrylamide),
Poly(N-methoxypropyl(meth)acrylamide)
, poly(N-ethoxypropyl(meth)acrylamide), poly(N-impropoxypropyl(meth)acrylamide), poly(N-ethoxyethyl(meth)acrylamide), poly(N-(2,2-dimethoxyethyl) N-methylacrylamide), poly(N-1methyl-2-methoxyethyl(meth)acrylamide), poly(N-1-methoxymethylpropyl(meth)acrylamide), poly(N-(1,3dioxolane-2- ylmethyl)-N-methylacrylamide), poly(N
-8-acryloyl 1,4-dioxa-8-aza-spiro[4.5]decane) and the like are known.

However, all of these heat-sensitive polymer compounds show heat sensitivity in an aqueous solution, but do not show heat sensitivity in other solvents. As a polymer that exhibits heat sensitivity in alcohol solvent, Bo! J(N-(1゜3-dioxolane-2
-ylmethyl)-N-methylacrylamide) and poly(
N-1,3-dioxy=3=solan-2-ylmethylacrylamide), which, unlike the above-mentioned heat-sensitive polymers, is insoluble at temperatures below the transition temperature and soluble at temperatures above the transition temperature ( Published patent gazette (
No. 1983-243112) and application (No. 2-72995
issue)).

[Problem to be solved by the invention]

Under these circumstances, an object of the present invention is to provide a raw material monomer for a thermosensitive polymer compound that undergoes a phase transition in water and alcohol solvents, in order to expand the range of use of thermosensitive polymer compounds. It was done for a purpose.

[Means to solve the problem]

As a result of intensive research to develop a heat-sensitive polymer compound that undergoes a phase transition in water and alcohol solvents, the present inventors conducted radical polymerization of a vinyl compound represented by CH2=CH -OH3 ○□CH2. It consists of a repeating unit represented by the formula -1←-CH2 CH-→-1 (C2 C! OCH2 ○□CH2, and 27
It has been discovered that a polymer compound having a molecular weight corresponding to an intrinsic viscosity [η] of 0.01 to 6.0 at a temperature of °C is a heat-sensitive polymer compound that undergoes a phase transition in water and alcohol solvents, Based on this knowledge, we have completed the present invention.

The vinyl compound of the present invention is a novel compound that has not been described in any literature, namely, N-methyl-N-2-(1,3-dioxolane-
2-yl)ethyl acrylamide, for example, according to the reaction formula: It can be obtained by reacting or by reacting acrylic acid chloride and N-methylaminoethyl 1,3-dioxolane in a solvent maintained at 0 to 10'C according to the reaction formula %. .

=9 The solvent used in the method of r et al. is not particularly limited as long as it is inert to acrylic acid chloride, and benzene, acetone, toluene, etc. are generally used. Regarding the reaction temperature, side reactions may occur if it is too high, so
It is preferable to carry out the reaction in the range of ~XO°C.

To isolate the target compound from the reaction mixture thus obtained, it is usually first carried out by filtration etc. to obtain triethylamine hydrochloride or N-methyl-2 aminoethyl-1,3
- After removing dioxolane hydrochloride, the solvent is distilled off from the filtrate using a rotary evaporator, and then purified by vacuum distillation using a conventional method. At this time, if necessary, vacuum distillation can be repeated to achieve high purity.

N-methyl-N-2-(1,3
-dioxolan-2-yl)ethyl acrylamide is (
Boiling point: 127°C/1 m m)] g) It is a colorless liquid and can be mixed with water, methyl alcohol, ethyl alcohol,
It is soluble in solvents such as acetone, tetrahydrofuran, chloroform, and Hensen, and insoluble in n-hexane and n-hebutane.

The vinyl compound of the present invention has CH2=Cl-1- group, C
Q N H- group, -CH2-〇- group, -CH< group, CH
Since it has three groups, etc., it can be identified by infrared absorption spectrum, mass spectrum, etc.

The heat-sensitive polymer compound of the present invention that undergoes a phase transition in water and an alcohol solvent can be produced by radical polymerizing the aforementioned N-methyl-N2-(1,3-dioxolan-2-yl)ethyl acrylamide. However, this polymerization is usually carried out by solution polymerization or bulk polymerization, using an azo compound such as benzoyl peroxide or peracetic acid as a polymerization initiator, or using active radiation such as ultraviolet rays, radiation, electron beams, or plasma. This can be done by irradiation.

The amount of the polymerization initiator used in this case is suitably in the range of 0.005 to 5% by weight, particularly 0.001 to 2% by weight, based on the weight of the monomer.

Particularly preferred is N-methyl N-2-
This is a method in which (1,3-dioxolan-2-yl)ethyl acrylamide is dissolved in an organic solvent at a concentration of 1 to 80% by weight and polymerized. The solvent used in such a solution polymerization method is not particularly limited as long as it dissolves in N-methyl-N-2-(1,3-dioxolan-2yl)ethyl acrylamide. For example, water, alcohols, acetone, tetrahydrofuran, chloroform, benzene, alkyl acetates, etc. may be used, and these may be used alone or in combination of two or more types depending on the case.

Regarding the degree of polymerization of the polymer compound obtained by radical polymerization of the vinyl compound of the present invention, the intrinsic viscosity [η] at a temperature of 27°C in an aqueous solution is 0.01 to 6.0.
is practical. Furthermore, regarding solubility in various solvents, cold water, methanol, acetone, benzene, tetrahydrofuran, methyl acetate, ethyl acetate,
Dissolves in hot alcohols, ethylene glycol, chloroform, etc., cold alcohols (excluding methanol),
It is insoluble in cyclohexane, n-hexane, n-hebutane hot water, etc.

The vinyl compound of the present invention is a novel vinyl compound that has not been described in any literature, and the polymer compound thereof is soluble in alcohol above the transition temperature, insoluble below the transition temperature, and soluble in water below the transition temperature, It also has the property of becoming insoluble above the transition temperature. For example, the transition temperature of a 1% alcohol solution of this polymer compound varies depending on the molecular weight, but it is 24 to 26 °C for ethanol and 16 to 26 °C for n-furopanol.
17°C1 iso70 panol 23-27°C, ter
The temperature is 40 to 41°C for t-amyl alcohol, and 20 to 22°C for isoamyl alcohol, and generally varies depending on the type of alcohol. Further, the transition temperature of a 1% aqueous solution is 65 to 78°C, although it varies depending on the molecular weight.

〔Effect of the invention〕

The vinyl compound of the present invention is a novel vinyl compound that has not been described in any literature. The polymer compound is a polymer compound that has not been described in literature, and is soluble in alcohol at high temperatures and insoluble in alcohol at low temperatures, soluble in water at temperatures below the transition temperature, and insoluble at temperatures above the transition temperature. It has the property of These polymers are used, for example, in light shielding materials such as greenhouses, temperature sensors, etc.
Furthermore, it can be used for toys, interior decoration, textile printing agents, displays, separation membranes, mechanochemical device materials, etc.

Next, the present invention will be explained in more detail with reference to Examples and Reference Examples, but the present invention is not limited to these Examples in any way.

〔Example〕

Triethylamine (39.27 g) was placed in a 2β Erlenmeyer flask.
), N-methyl-2-aminoethyl-1,3 dioxolane (50.84 g) and benzene (431 ml), cooled with water and kept the content at a temperature of 10 ° C or less,
While stirring, acrylic acid chloride (31mk) diluted with benzene (69rr+&) was slowly added dropwise from the dropping funnel over about 3 hours. After completing the dropwise addition, the reaction solution was left in the refrigerator overnight to complete the reaction, filtered, and benzene was distilled off using a rotary evaporator to obtain crude N-
Methyl-N-2-(1゜3-dioxolan-2-yl)
Ethylacrylamide was concentrated. Then, vacuum distillation was carried out using a conventional method to obtain 57.24 g of a liquid substance with a boiling point of 127°C/l mm Hg.

The infrared absorption spectrum of this substance is shown in FIG. 1, and the mass spectrum is shown in FIG. 3.

The results of these spectral analyzes are as follows.

Infrared spectrum analysis: H CH2=CH >C=O >CH-= =34 to 16 =11 =16 2 9 3 5°Ocm-'7cm-'Ocm-'2cm-' 8 8 0 am-' = 15- Mass spectrum analysis: m/e M+1 = 186 ○ CH2 CH2= CI (C○ = 130 H2 0-CH2 0-CH2 CH2=CH-CC)-=55 CH2=CT-T-=27 From the above analysis results, It was confirmed to be N-methyl-N-21,3-dioxolan-2-yl)ethyl acrylamide.

[Reference Example 1] A polymer compound of the vinyl monomer obtained in the example was produced.

27.82 g of N-methyl-N-2-(13-dioxolan-2-yl)ethyl acrylamide was placed in a 500 ml Erlenmeyer flask with a U-tube fitted with a capillary stopper.
200ml of benzene (175°27g) and A
15 g of IB No. was added and nitrogen gas was vigorously bubbled through for 30 minutes. Then, it was heated at 60°C for 30 minutes under a nitrogen stream.
This was done by heating for a period of time.

The resulting polymer was isolated by mixing it in n-hexane with the reaction solvent.

Yield - 25,72 g.

The infrared absorption spectrum of this polymer compound is shown in FIG. By comparing the infrared absorption spectrum of the vinyl monomer with that of the polymer compound, it was confirmed that the vinyl group of 1607CM-' disappeared and a polymer compound was formed.

The obtained polymer compound was made into an aqueous solution, and the viscosity was measured at 27°C using an Ubbelohde viscometer, and the intrinsic viscosity [
η] was calculated.

Intrinsic viscosity [η] = 0.73°.Thermal sensitivity characteristics were also investigated by measuring the light transmittance of an aqueous solution or an alcoholic solution under thermal stimulation.

The light transmittance at a wavelength of 500 nm of a 1% concentration polymer compound aqueous solution or alcohol solution was measured using a spectrophotometer with a temperature controller at a heating rate of 1°C/min and a cooling rate of 1°C/min. . The transition temperature was determined from the temperature (T L) at which the light transmittance at the time of heating up for an aqueous solution or the light transmittance at the time of falling R for an alcohol solution was 0.5 of the initial transmittance.

Transition temperature of aqueous solution: 78°C0 Among these, the transition temperature of alcoholic solution is shown in Table 1.

Table 1 [Reference Example 2] N-Methyl-N-2-(1°3-dioxolan-2-yl)ethyl acrylamide 11.04. g
, 150.36 g of water was added, and nitrogen gas was vigorously bubbled through for 30 minutes. Next, 15.0 mg of ammonium persulfate was added at 60° C. under a nitrogen stream at +t+ to initiate polymerization, which was heated for 4 hours. The resulting polymer was isolated by mixing it in n-hexane with the reaction solvent.

Yield -11.03g0 The formation of a polymer compound was confirmed in the same manner as in Reference Example 1, and the intrinsic viscosity [η] at 27°C in an aqueous solution was 0.58. The transition temperature was determined.

Transition temperature of aqueous solution: 65.5°C6 Of these, the transition temperature of alcoholic solution is shown in Table 2.

Table 2 (%) Kinkaku r

[Brief explanation of drawings]

FIG. 1 shows the infrared absorption spectrum of the vinyl monomer of Example, FIG. 2 shows the infrared absorption spectrum of the polymer compound of Reference Example 1, and FIG. 3 shows the mass spectrum of the vinyl monomer of Example. Patent applicant: Director of the Agency of Industrial Science and Technology Ken Sugiura (%) Yusei Town

Claims (1)

[Claims] formula ▲Contains mathematical formulas, chemical formulas, tables, etc.▼ A vinyl compound represented by